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WO2015141676A1 - 熱サイクル用作動媒体、熱サイクルシステム用組成物および熱サイクルシステム - Google Patents

熱サイクル用作動媒体、熱サイクルシステム用組成物および熱サイクルシステム Download PDF

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Publication number
WO2015141676A1
WO2015141676A1 PCT/JP2015/057899 JP2015057899W WO2015141676A1 WO 2015141676 A1 WO2015141676 A1 WO 2015141676A1 JP 2015057899 W JP2015057899 W JP 2015057899W WO 2015141676 A1 WO2015141676 A1 WO 2015141676A1
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Prior art keywords
working medium
hfo
heat
mass
heat cycle
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PCT/JP2015/057899
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English (en)
French (fr)
Japanese (ja)
Inventor
正人 福島
聡史 河口
勝也 上野
田中　俊幸
岡本　秀一
哲央 大塚
宜伸 門脇
達弘 野上
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旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to EP15765774.3A priority Critical patent/EP3121243A4/de
Priority to JP2016508736A priority patent/JP6493388B2/ja
Priority to CN201580014147.9A priority patent/CN106255736B/zh
Publication of WO2015141676A1 publication Critical patent/WO2015141676A1/ja
Priority to US15/252,996 priority patent/US10144856B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B31/00—Compressor arrangements
    • F25B31/002—Lubrication
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
    • F25B43/02—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat for separating lubricants from the refrigerant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2500/00—Problems to be solved
    • F25B2500/14—Problems to be solved the presence of moisture in a refrigeration component or cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2500/00—Problems to be solved
    • F25B2500/22—Preventing, detecting or repairing leaks of refrigeration fluids
    • F25B2500/222—Detecting refrigerant leaks

Definitions

  • the present invention relates to a thermal cycle working medium, a thermal cycle system composition including the same, and a thermal cycle system using the composition.
  • a working medium for heat cycle such as a refrigerant for a refrigerator, a refrigerant for an air conditioner, a working medium for a power generation system (waste heat recovery power generation, etc.), a working medium for a latent heat transport device (heat pipe, etc.), a secondary cooling medium, etc.
  • chlorofluorocarbons such as chlorotrifluoromethane and dichlorodifluoromethane
  • HCFC hydrochlorofluorocarbons
  • chlorodifluoromethane chlorodifluoromethane
  • HFC-32 difluoromethane
  • HFC-125 pentafluoroethane
  • HFC-125 hydrofluorocarbons
  • R410A a quasi-azeotropic refrigerant mixture having a mass ratio of 1: 1 between HFC-32 and HFC-125 is a refrigerant that has been widely used.
  • HFC may cause global warming.
  • R410A has been widely used for ordinary air-conditioning equipment called so-called package air conditioners and room air conditioners because of its high refrigerating capacity.
  • GWP global warming potential
  • the global warming potential (GWP) is as high as 2088, and therefore development of a low GWP working medium is required.
  • Patent Document 1 discloses a technique related to a working medium using trifluoroethylene (HFO-1123) that has the above-described characteristics and can obtain excellent cycle performance. .
  • HFO-1123 trifluoroethylene
  • Patent Document 1 an attempt is made to use HFO-1123 in combination with various HFCs as a working medium in order to further improve the nonflammability and cycle performance of the working medium.
  • Non-Patent Document 1 reports an attempt to suppress the self-decomposition reaction by mixing HFO-1123 with other components such as vinylidene fluoride to reduce the content of HFO-1123. ing.
  • HFO-1234yf 2,3,3,3-tetrafluoropropene
  • Patent Document 2 describes a composition containing HFO-1234yf obtained when HFO-1234yf is produced by a specific method.
  • the composition described in Patent Document 2 includes many compounds, including a composition containing HFO-1234yf and HFO-1123.
  • HFO-1123 is only described together with many other compounds as a by-product of HFO-1234yf, and it is not disclosed that a composition in which both are mixed at a specific ratio is used as a working medium.
  • the present inventors diligently studied to solve the above-mentioned problems, and found that by combining HFO-1123 with HFO-1234yf at a specific ratio, a working medium for heat cycle having good characteristics can be obtained.
  • the present invention has been completed.
  • the ratio of the total amount of the trifluoroethylene and the 2,3,3,3-tetrafluoropropene to the total amount of the working medium for the heat cycle is more than 97% by mass and 100% by mass or less.
  • a composition for a heat cycle system comprising the heat cycle working medium according to any one of [1] to [4] and a refrigerating machine oil.
  • the thermal cycle system according to [6] which is a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.
  • the thermal cycle system of the present invention by using the composition for the thermal cycle system of the present invention, it has practical thermal cycle performance and good durability while suppressing the influence on global warming. Can provide a stable thermal cycle system.
  • the working medium of the present invention is a working medium for heat cycle containing HFO-1123 and HFO-1234yf, and the total amount of HFO-1123 and HFO-1234yf contained in the working medium is 90% by mass. It is a working medium for a heat cycle in which the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234yf is 21% by mass to 39% by mass.
  • a heat cycle using a heat exchanger such as a condenser or an evaporator can be used without any particular limitation.
  • the working medium for heat cycle of the present invention is a mixed medium containing HFO-1123, HFO-1234yf, and other components as required.
  • the global warming potential (100 years) of HFO-1234yf is 4 according to the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007), and global warming of HFO-1123
  • IPCC Intergovernmental Panel on Climate Change
  • the coefficient (100 years) is 0.3 as a value measured according to the IPCC Fourth Assessment Report.
  • GWP is a value of 100 years in the IPCC Fourth Assessment Report unless otherwise specified.
  • GWP in a mixture is shown as a weighted average by a composition mass.
  • the working medium of the present invention contains HFO-1123 and HFO-1234yf with extremely low GWP in excess of 90% by mass, and the GWP value of the obtained working medium can be low.
  • the GWP of the other component is higher than HFO-1123 and HFO-1234yf as in, for example, a saturated HFC described later, the composition becomes lower as the content ratio is lower.
  • a highly durable working medium for thermal cycle is obtained by using a composition that does not have self-decomposability at about 7.0 MPa. Can be obtained.
  • the working medium for heat cycle of the present invention can be used in a heat cycle system even if it has a self-decomposable composition, depending on the use conditions, with careful handling.
  • the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234yf in the working medium is in the range of 21% by mass or more, a practical coefficient of performance and refrigeration capacity can be secured. A range of 23% by mass or more is preferable because the coefficient of performance is further improved. Further, if the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234yf in the working medium is in the range of 39% by mass or less, there is no self-decomposability under the temperature conditions when applied to a thermal cycle system, A working medium for heat cycle having excellent durability can be obtained.
  • HFO-1123 and HFO-1234yf constituting the working medium of the present invention are both HFO and are compounds having little influence on global warming.
  • HFO-1123 is excellent in ability as a working medium, but may not be sufficient in comparison with other HFOs in terms of coefficient of performance.
  • HFO-1123 is used alone, under high pressure conditions, the durability as a working medium is low due to self-decomposition, and the service life may be extremely shortened.
  • the working medium for heat cycle of the present invention is a practical working medium with improved characteristics by mixing at a specific ratio, which is not practically used alone, as described above. is there.
  • the working medium for heat cycle of the present invention may optionally contain a compound used as a normal working medium in addition to HFO-1123 and HFO-1234yf as long as the effects of the present invention are not impaired.
  • HFC 1,1-difluoroethane
  • HFC-152a 1,1,1-trifluoroethane
  • HFC-150 1,1,2,2-tetrafluoroethane
  • HFC-125 1,1,2,2-tetrafluoroethane
  • HFC-32, HFC -134a, and HFC-125 are more preferred.
  • One HFC may be used alone, or two or more HFCs may be used in combination.
  • HFO HFO other than HFO-1123 and HFO-1234yf
  • HFO-1234yf HFO other than HFO-1123 and HFO-1234yf
  • HFO-1243zf trans-1,2-difluoroethylene
  • HFO-1261yf 1,1,2-trifluoropropene
  • HFO-1243yc 2-fluoropropene
  • HFO-1225ye HFO-1225ye
  • HFO-1225ye cis-1,2,3,3 3-pentafluoropropene
  • HFO-1234ze (E)) trans-1,3,3,3-tetrafluoropropene
  • HFO-1234ze (Z) 3,3,3-trifluoropropene (HFO-1243zf) and the like.
  • HFO-1234ze (E) and HFO-1234ze (Z) are preferable as HFO, which is an optional component, because it has a high critical temperature and is excellent in safety and coefficient of performance.
  • HFO-1234ze (E) is preferable. More preferred.
  • HFOs other than HFO-1123 and HFO-1234yf may be used alone or in combination of two or more.
  • the working fluid for heat cycle of the present invention contains HFC and / or HFO other than HFO-1123 and HFO-1234yf as optional components, HFC and HFO-1123 and HFO-1234yf in 100% by mass of the working medium
  • the total content of HFO other than the above is 10% by mass or less, preferably 1 to 10% by mass, more preferably 1 to 7% by mass, and further preferably 2 to 7% by mass.
  • the total content of HFC other than HFC and HFO-1123 and HFO-1234yf in the working medium is appropriately adjusted within the above range depending on the type of HFO other than HFC, HFO-1123 and HFO-1234yf used. .
  • the temperature gradient is lowered, the capacity is improved or the efficiency is further increased, and further, the global warming coefficient is taken into consideration. .
  • the working medium for heat cycle of the present invention may contain carbon dioxide, hydrocarbon, chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), etc. as other optional components in addition to the above optional components.
  • CFO chlorofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • Other optional components are preferably components that have a small effect on the ozone layer and a small effect on global warming.
  • hydrocarbon examples include propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like.
  • a hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.
  • CFO examples include chlorofluoropropene and chlorofluoroethylene.
  • CFO 1,1-dichloro-2,3,3,3-tetrafluoropropene (from which it is easy to suppress the flammability of the working medium without greatly reducing the cycle performance of the working medium for heat cycle of the present invention, CFO-1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) and 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are preferred.
  • One type of CFO may be used alone, or two or more types may be used in combination.
  • the working medium for heat cycle of the present invention contains CFO
  • the content thereof is 10% by weight or less, preferably 1 to 10% by weight, preferably 1 to 7% by weight with respect to 100% by weight of the working medium. More preferred is 2 to 7% by mass. If the CFO content is at least the lower limit value, it is easy to suppress the combustibility of the working medium. If the content of CFO is not more than the upper limit value, good cycle performance can be easily obtained.
  • HCFO examples include hydrochlorofluoropropene and hydrochlorofluoroethylene.
  • HCFO 1-chloro-2,3,3,3-tetrafluoropropene (HCFO--) can be used to suppress the flammability of the working medium without greatly reducing the cycle performance of the working medium for heat cycle of the present invention. 1224yd), 1-chloro-1,2-difluoroethylene (HCFO-1122).
  • HCFO may be used alone or in combination of two or more.
  • the content of HCFO in 100% by weight of the working medium is 10% by weight or less, preferably 1 to 10% by weight, more preferably 1 to 7% by weight. Preferably, 2 to 7% by mass is more preferable. If the content of HCFO is equal to or higher than the lower limit value, it is easy to suppress the combustibility of the working medium. If the content of HCFO is not more than the upper limit value, good cycle performance can be easily obtained.
  • the working medium for heat cycle of the present invention contains the above-mentioned optional components and other optional components, the total content is 10% by mass or less with respect to 100% by mass of the working medium.
  • the above-described working medium for heat cycle according to the present invention is an HFO that has little influence on global warming, and has a good balance between HFO-1123, which is excellent as a working medium, and the ability and efficiency as a working medium.
  • HFO-1234yf can be obtained by mixing both at a specific ratio.
  • the working medium for heat cycle of the present invention obtained in this way is obtained in combination with the ratio of ensuring the cycle performance, taking into consideration the durability, and to the global warming It has practical cycle performance while suppressing the influence.
  • composition for thermal cycle system Composition for thermal cycle system
  • the heat cycle working medium of the present invention can be used as a composition for a heat cycle system of the present invention, usually mixed with refrigeration oil when applied to a heat cycle system.
  • the composition for a heat cycle system of the present invention may further contain known additives such as a stabilizer and a leak detection substance.
  • refrigerator oil As the refrigerating machine oil, a known refrigerating machine oil used for a composition for a heat cycle system can be employed without particular limitation, together with a working medium made of a halogenated hydrocarbon. Specific examples of the refrigerating machine oil include oxygen-containing refrigerating machine oil (ester refrigerating machine oil, ether refrigerating machine oil, etc.), fluorine refrigerating machine oil, mineral refrigerating machine oil, hydrocarbon refrigerating machine oil, and the like.
  • ester refrigerating machine oils include dibasic acid ester oils, polyol ester oils, complex ester oils, and polyol carbonate oils.
  • the dibasic acid ester oil includes a dibasic acid having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a carbon number having a linear or branched alkyl group.
  • Esters with 1 to 15 monohydric alcohols methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc. are preferred.
  • dibasic acid ester oil examples include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.
  • Polyol ester oils include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentadiol, neopentyl glycol, 1,7- Heptanediol, 1,12-dodecanediol, etc.) or polyol having 3 to 20 hydroxyl groups (trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensate, etc.); Fatty acids having 6 to 20 carbon atoms (hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid,
  • Polyol ester oils include esters of hindered alcohols (neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, etc.) (trimethylol propane tripelargonate, pentaerythritol 2-ethylhexanoate). And pentaerythritol tetrapelargonate) are preferred.
  • hindered alcohols neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, etc.
  • trimel propane tripelargonate pentaerythritol 2-ethylhexanoate
  • pentaerythritol tetrapelargonate are preferred.
  • the complex ester oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol.
  • fatty acid, dibasic acid, monohydric alcohol, and polyol the same ones as described above can be used.
  • the polyol carbonate oil is an ester of carbonic acid and polyol.
  • examples of the polyol include the same diol as described above and the same polyol as described above.
  • the polyol carbonate oil may be a ring-opening polymer of cyclic alkylene carbonate.
  • ether refrigerating machine oil examples include polyvinyl ether oil and polyoxyalkylene oil.
  • polyvinyl ether oil examples include those obtained by polymerizing vinyl ether monomers such as alkyl vinyl ethers, and copolymers obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having an olefinic double bond.
  • a vinyl ether monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • hydrocarbon monomers having an olefinic double bond examples include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, various alkyl-substituted styrenes, etc. Is mentioned.
  • the hydrocarbon monomer which has an olefinic double bond may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polyvinyl ether copolymer may be either a block or a random copolymer.
  • a polyvinyl ether oil may be used individually by 1 type, and may be used in combination of 2 or more type.
  • polyoxyalkylene oil examples include polyoxyalkylene monools, polyoxyalkylene polyols, alkyl etherified products of polyoxyalkylene monools and polyoxyalkylene polyols, and esterified products of polyoxyalkylene monools and polyoxyalkylene polyols.
  • Polyoxyalkylene monools and polyoxyalkylene polyols are used to open a C 2-4 alkylene oxide (ethylene oxide, propylene oxide, etc.) in an initiator such as water or a hydroxyl group-containing compound in the presence of a catalyst such as an alkali hydroxide. Examples thereof include those obtained by a method of addition polymerization.
  • the oxyalkylene units in the polyalkylene chain may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.
  • the initiator used for the reaction examples include water, monohydric alcohols such as methanol and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerol.
  • the polyoxyalkylene oil is preferably an alkyl etherified product or an esterified product of polyoxyalkylene monool or polyoxyalkylene polyol.
  • the polyoxyalkylene polyol is preferably polyoxyalkylene glycol.
  • an alkyl etherified product of polyoxyalkylene glycol in which the terminal hydroxyl group of polyoxyalkylene glycol is capped with an alkyl group such as a methyl group, called polyglycol oil is preferable.
  • fluorinated refrigerating machine oil examples include compounds in which hydrogen atoms of synthetic oils (mineral oil, poly ⁇ -olefin, alkylbenzene, alkylnaphthalene, etc. described later) are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, and the like.
  • mineral-based refrigeration oil refrigerating machine oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil is refined (solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation) Paraffinic mineral oil, naphthenic mineral oil, etc., which are refined by appropriately combining refining, clay treatment, etc.).
  • hydrocarbon refrigerating machine oil examples include poly ⁇ -olefin, alkylbenzene, alkylnaphthalene and the like.
  • Refrigerating machine oil may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the refrigerating machine oil is preferably at least one selected from polyol ester oil, polyvinyl ether oil, and polyglycol oil from the viewpoint of compatibility with the working medium.
  • the amount of the refrigerating machine oil may be within a range that does not significantly reduce the effect of the present invention, and is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the working medium.
  • a stabilizer is a component that improves the stability of the working medium against heat and oxidation.
  • a known stabilizer used in a heat cycle system together with a working medium composed of a halogenated hydrocarbon, for example, an oxidation resistance improver, a heat resistance improver, a metal deactivator, etc. is not particularly limited. Can be adopted.
  • oxidation resistance improver and heat resistance improver examples include N, N′-diphenylphenylenediamine, p-octyldiphenylamine, p, p′-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine.
  • the oxidation resistance improver and the heat resistance improver may be used alone or in combination of two or more.
  • Metal deactivators include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimercaptothiadiazole, salicyridin-propylenediamine, pyrazole, benzotriazole, toltriazole, 2-methylbenzimidazole, 3,5-dimethyl Of pyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Examples thereof include amine salts and derivatives thereof.
  • the addition amount of the stabilizer may be in a range that does not significantly reduce the effect of the present invention, and is preferably 5 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the working medium.
  • leak detection substance examples include ultraviolet fluorescent dyes, odorous gases and odor masking agents.
  • the ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T 2007-511645, JP-T 2008-500437, JP-T 2008-531836.
  • odor masking agent examples include known fragrances used in heat cycle systems, together with working media composed of halogenated hydrocarbons, such as those described in JP-T-2008-500337 and JP-A-2008-531836. Can be mentioned.
  • a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
  • solubilizer examples include those described in JP-T 2007-511645, JP-T 2008-500337, JP-T 2008-531836.
  • the addition amount of the leak detection substance may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the working medium.
  • the thermal cycle system of the present invention is a system using the working medium for thermal cycle of the present invention.
  • the working medium for heat cycle of the present invention When applying the working medium for heat cycle of the present invention to a heat cycle system, it is usually applied as a composition for a heat cycle system containing the working medium.
  • the heat cycle system of the present invention may be a heat pump system that uses warm heat obtained by a condenser, or may be a refrigeration cycle system that uses cold heat obtained by an evaporator.
  • thermal cycle system of the present invention examples include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers.
  • the thermal cycle system of the present invention can stably exhibit thermal cycle performance even in a higher temperature operating environment, it is preferably used as an air conditioner that is often installed outdoors.
  • the thermal cycle system of the present invention is also preferably used as a refrigeration / refrigeration apparatus.
  • air conditioners include room air conditioners, packaged air conditioners (store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.
  • refrigeration / refrigeration equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.
  • a power generation system using a Rankine cycle system is preferable.
  • the working medium is heated by geothermal energy, solar heat, waste heat in the middle to high temperature range of about 50 to 200 ° C in the evaporator, and the working medium turned into high-temperature and high-pressure steam is expanded.
  • An example is a system in which power is generated by adiabatic expansion by a machine, and a generator is driven by work generated by the adiabatic expansion.
  • the heat cycle system of the present invention may be a heat transport device.
  • a latent heat transport device is preferable.
  • Examples of the latent heat transport device include a heat pipe and a two-phase sealed thermosyphon device that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device.
  • the heat pipe is applied to a relatively small cooling device such as a cooling device for a heat generating part of a semiconductor element or an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for a gas-gas heat exchanger, for promoting snow melting on roads, and for preventing freezing.
  • the refrigeration cycle system is a system that uses cold heat obtained by an evaporator.
  • a refrigeration cycle system 10 shown in FIG. 1 cools and liquefies a compressor 11 that compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B and the working medium vapor B discharged from the compressor 11.
  • the condenser 12 as a low-temperature and high-pressure working medium C
  • the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D
  • the working medium D discharged from the expansion valve 13 Is composed of an evaporator 14 that heats the working medium vapor A to a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12.
  • the working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D (hereinafter referred to as “CD process”).
  • the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become the load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).
  • the refrigeration cycle system 10 is a cycle system including adiabatic / isoentropic change, isoenthalpy change, and isopressure change.
  • the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be expressed as a trapezoid having A, B, C, and D as apexes.
  • the AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium vapor A into the high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG.
  • the BC process is a process in which the condenser 12 performs isobaric cooling to convert the high-temperature and high-pressure working medium vapor B into a low-temperature and high-pressure working medium C, and is indicated by a BC line in FIG.
  • the pressure at this time is the condensation pressure.
  • Pressure - an intersection T 1 of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T 2 is the condensation boiling temperature.
  • the temperature gradient of a non-azeotropic mixed medium such as a mixed medium of HFO-1123 and HFO-1234yf is shown as a difference between T 1 and T 2 .
  • the CD process is a process in which isenthalpy expansion is performed by the expansion valve 13 and the low-temperature and high-pressure working medium C is used as the low-temperature and low-pressure working medium D, and is indicated by a CD line in FIG.
  • T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (hereinafter, optionally in the "SC" It is shown.)
  • the DA process is a process of performing isobaric heating in the evaporator 14 to return the low-temperature and low-pressure working medium D to the high-temperature and low-pressure working medium vapor A, and is indicated by a DA line in FIG.
  • the pressure at this time is the evaporation pressure.
  • Pressure - intersection T 6 of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in T 7, T 7 -T 6 is (i) ⁇ superheat of the working medium in the cycle of (iv) a (hereinafter,. Indicated by "SH", if necessary) .
  • T 4 indicates the temperature of the working medium D.
  • the cycle performance of the working medium is evaluated by, for example, the refrigerating capacity of the working medium (hereinafter, indicated as “Q” as necessary) and the coefficient of performance (hereinafter, indicated as “COP” as necessary).
  • Q and COP of the working medium in each state of A after evaporation, high temperature and low pressure
  • B after compression, high temperature and high pressure
  • C after condensation, low temperature and high pressure
  • D after expansion, low temperature and low pressure.
  • COP means efficiency in the refrigeration cycle system. The higher the COP value, the smaller the input, for example, the amount of power required to operate the compressor, and the larger the output, for example, Q can be obtained. It represents what you can do.
  • Q means the ability to freeze the load fluid, and the higher Q means that more work can be done in the same system.
  • a large Q indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
  • R410A HFC- It is possible to set both Q and COP at a practical level while keeping the global warming coefficient much lower than when using a mixed medium of 32 and HFC-125 (mass ratio of 1: 1). is there.
  • a method for controlling the moisture concentration in the thermal cycle system a method using a moisture removing means such as a desiccant (silica gel, activated alumina, zeolite, lithium chloride, etc.) can be mentioned.
  • the desiccant is preferably brought into contact with a liquid working medium from the viewpoint of dehydration efficiency. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or at the inlet of the evaporator 14 to contact the working medium.
  • a zeolitic desiccant is preferable from the viewpoint of the chemical reactivity between the desiccant and the working medium and the moisture absorption capacity of the desiccant.
  • the main component is a compound represented by the following formula (3) from the viewpoint of excellent hygroscopic capacity. Zeolite desiccants are preferred.
  • M is a Group 1 element such as Na or K, or a Group 2 element such as Ca
  • n is the valence of M
  • x and y are values determined by the crystal structure.
  • pore diameter and breaking strength are important.
  • the working medium is adsorbed in the desiccant, resulting in a chemical reaction between the working medium and the desiccant, and generation of a non-condensable gas.
  • Undesirable phenomena such as a decrease in the strength of the desiccant and a decrease in the adsorption capacity will occur.
  • a zeolitic desiccant having a small pore size as the desiccant.
  • a sodium / potassium A type synthetic zeolite having a pore diameter of 3.5 angstroms or less is preferable.
  • the size of the zeolitic desiccant is preferably about 0.5 to 5 mm because if it is too small, it will cause clogging of valves and piping details of the heat cycle system, and if it is too large, the drying ability will be reduced.
  • the shape is preferably granular or cylindrical.
  • the zeolitic desiccant can be formed into an arbitrary shape by solidifying powdery zeolite with a binder (such as bentonite). Other desiccants (silica gel, activated alumina, etc.) may be used in combination as long as the zeolitic desiccant is mainly used.
  • the use ratio of the zeolitic desiccant with respect to the working medium is not particularly limited.
  • the water concentration in the heat cycle system is preferably less than 10,000 ppm, more preferably less than 1000 ppm, and particularly preferably less than 100 ppm in terms of mass ratio with respect to the working medium for heat cycle.
  • Non-condensable gas concentration Furthermore, when non-condensable gas is mixed in the heat cycle system, it adversely affects heat transfer in the condenser and the evaporator and increases in operating pressure. Therefore, it is necessary to suppress mixing as much as possible.
  • oxygen which is one of non-condensable gases, reacts with the working medium and refrigerating machine oil to promote decomposition.
  • the non-condensable gas concentration is preferably less than 10,000 ppm, more preferably less than 1000 ppm, and particularly preferably less than 100 ppm in terms of mass ratio with respect to the heat cycle working medium.
  • the presence of chlorine in the heat cycle system has undesirable effects such as deposit formation due to reaction with metals, wear of bearings, decomposition of heat cycle working medium and refrigeration oil.
  • the chlorine concentration in the heat cycle system is preferably 100 ppm or less, and particularly preferably 50 ppm or less in terms of a mass ratio with respect to the heat cycle working medium.
  • Metal concentration The presence of metals such as palladium, nickel, and iron in the thermal cycle system has undesirable effects such as decomposition and oligomerization of HFO-1123.
  • the metal concentration in the heat cycle system is preferably 5 ppm or less, particularly preferably 1 ppm or less, in terms of a mass ratio with respect to the heat cycle working medium.
  • the presence of acid in the thermal cycle system has undesirable effects such as acceleration of oxidative decomposition and self-decomposition of HFO-1123.
  • the acid content concentration in the heat cycle system is preferably 1 ppm or less, particularly preferably 0.2 ppm or less, in terms of a mass ratio with respect to the heat cycle working medium.
  • the presence of metal powder, other oils other than refrigerating machine oil, and high-boiling residues in the heat cycle system adversely affects the clogging of the vaporizer and increased resistance of the rotating part.
  • the residue concentration in the heat cycle system is preferably 1000 ppm or less, and particularly preferably 100 ppm or less in terms of mass ratio with respect to the heat cycle working medium.
  • the residue can be removed by filtering the working medium for the heat cycle system with a filter or the like.
  • each component (HFO-1123, HFO-1234yf, etc.) of the working medium for the heat cycle system is filtered to remove the residue, and then mixed. It is good also as a working medium for heat cycle systems.
  • thermal cycle system of the present invention by using the composition for the thermal cycle system of the present invention, practical cycle performance is obtained while suppressing the influence on global warming, and durability is improved. It can be expensive.
  • Examples 1 to 4 are examples, and examples 5 to 8 are comparative examples.
  • Examples 1 to 8 According to a conventional method, HFO-1123 and HFO-1234yf were mixed at the ratios shown in Table 1 to obtain working media for thermal cycling (Examples 1 to 8). The ratio of the total amount of HFO-1123 and HFO-1234yf in the total amount of the working medium is 100% by mass.
  • Examples 1 to 8 of the working medium were sealed up to the pressure shown in Table 2 in a spherical pressure vessel with an internal volume of 650 cm 3 in which the temperature inside the reactor was controlled in the range of 190 ° C. to 210 ° C. by heating with an external heater. . Thereafter, a platinum wire (outer diameter 0.5 mm, length 25 mm) installed inside the spherical pressure vessel was melted by a voltage and current of 10 V, 50 A (hot wire method). The temperature and pressure change in the pressure vessel generated after fusing was measured. Moreover, the gas composition after the test was analyzed.
  • FIG. 3 is a graph showing the presence or absence of self-decomposability in the relationship between the content of HFO-1123 in the working medium and the pressure.
  • the pressure is 5 MPa or less.
  • the working medium having a composition of less than 35% by mass does not have self-decomposing property at a pressure of 7 MPa or less.
  • the continuous line shown in FIG. 3 is an auxiliary line estimated with respect to the boundary of the presence or absence of self-degradability about the working medium of a present Example.
  • Refrigeration cycle performance (capacity and efficiency) as the cycle performance (capacity and efficiency) is performed for the case where isothermal cooling by the condenser 12 is performed in the process, isoenthalpy expansion by the expansion valve 13 is performed in the CD process, and isobaric heating is performed by the evaporator 14 in the DA process. Refrigeration capacity and coefficient of performance) were evaluated.
  • the average evaporation temperature of the working medium for heat cycle in the evaporator 14 is 0 ° C.
  • the average condensation temperature of the working medium for heat cycle in the condenser 12 is 40 ° C.
  • the degree of supercooling of the working medium for heat cycle in the condenser 12 is evaluated.
  • the degree of superheat of the working medium for heat cycle in the evaporator 14 was 5 ° C.
  • the refrigeration capacity and the coefficient of performance are A (after evaporation, high temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (after expansion, low temperature and low pressure).
  • A after evaporation, high temperature and low pressure
  • B after compression, high temperature and high pressure
  • C after condensation, low temperature and high pressure
  • D after expansion, low temperature and low pressure
  • Thermodynamic properties necessary for calculation of the refrigeration cycle performance were calculated based on a generalized equation of state (Soave-Redrich-Kwong equation) based on the corresponding state principle and thermodynamic relational equations. When characteristic values were not available, calculations were performed using an estimation method based on the group contribution method.
  • the refrigeration capacity and the coefficient of performance were obtained as relative ratios when the refrigeration capacity and the coefficient of performance of R410A were each 1.000.
  • the GWP of the working medium was determined as a weighted average based on the composition mass based on the GWP of each compound as a raw material (0.3 for HFO-1123 and 4 for HFO-1234yf). That is, the GWP of the working medium was determined by dividing the sum of the product of mass% and GWP of each compound constituting the working medium by 100.
  • Table 3 shows the results of the freezing capacity (vs. R410A) and the coefficient of performance (vs. R410A), and the GWP calculation results.
  • the coefficient of performance equivalent to or higher than that of R410A is obtained in the working medium for heat cycle of the present invention, and the refrigerating capacity is lower than that of R410A, but is in a practical range.
  • the practical range here means that the refrigerating capacity is 0.590 or more as compared with R410A, and in this range, it can be used as a working medium for thermal cycle.
  • the coefficient of performance was improved by including HFO-1123 and HFO-1234yf as compared with HFO-1123 alone. It can also be seen that GWP is also low.
  • the working media of Examples 1 to 4 which are embodiments of the present invention have a low GWP, practical cycle performance based on R410A, and self-decomposability even when in a high pressure state. It was found that the working medium has excellent durability that can be suppressed.
  • the working medium of the present invention includes refrigerants for refrigeration / refrigeration equipment (built-in showcases, separate-type showcases, commercial refrigeration / refrigerators, vending machines, ice machines, etc.), air conditioning equipment (room air conditioners, store packaged air conditioners, Package air conditioners for buildings, packaged air conditioners for facilities, gas engine heat pumps, air conditioners for trains, air conditioners for automobiles, etc.) refrigerants, working fluids for power generation systems (waste heat recovery power generation, etc.), heat transport devices (heat pipes, etc.) It is useful as a working medium and a medium for a secondary cooler.
  • refrigerants for refrigeration / refrigeration equipment built-in showcases, separate-type showcases, commercial refrigeration / refrigerators, vending machines, ice machines, etc.
  • air conditioning equipment room air conditioners, store packaged air conditioners, Package air conditioners for buildings, packaged air conditioners for facilities, gas engine heat pumps, air conditioners for trains, air conditioners for automobiles, etc.
  • refrigerants working fluids for power generation

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